CN210419465U - Desulfurization wastewater pretreatment device - Google Patents
Desulfurization wastewater pretreatment device Download PDFInfo
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- CN210419465U CN210419465U CN201720925966.5U CN201720925966U CN210419465U CN 210419465 U CN210419465 U CN 210419465U CN 201720925966 U CN201720925966 U CN 201720925966U CN 210419465 U CN210419465 U CN 210419465U
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Abstract
The utility model provides a device of desulfurization waste water preliminary treatment. Comprises the following steps arranged along the flow direction of the desulfurization wastewater: the first-stage reactor is provided with a barium hydroxide adding unit and an organic sulfur or sulfide adding unit; the secondary reactor is provided with a barium salt adding unit. By optimizing the softening pretreatment process method before the desulfurization wastewater is subjected to evaporative crystallization, the cost for treating the desulfurization wastewater by adopting the evaporative crystallization method can be effectively reduced. In addition, a device is provided, and the positions of the organic sulfur or sulfide adding unit and the barium salt adding unit are exchanged.
Description
Technical Field
The utility model belongs to the technical field of the environmental protection, concretely relates to desulfurization waste water preliminary treatment's device.
Background
Coal-fired power generation plays an important role in energy supply in China. In order to protect the atmospheric environment, most of the power plants in China in recent years adopt a limestone-gypsum wet desulphurization technology for removing sulfur dioxide in flue gas. The wet desulphurization wastewater of the coal-fired power plant has complex components and contains high-concentration suspended matters, supersaturated sulfite, chloride ions, sulfate and a plurality of heavy metals. At present, desulfurization wastewater is mainly treated by a chemical precipitation method, part of indexes are difficult to reach the standard, even after the desulfurization wastewater reaches the standard, the salt content of effluent is still 2% -4% due to the existence of a large amount of sulfate and chloride in the wastewater, the effluent is difficult to be recycled, and surface water and soil ecology are damaged after the desulfurization wastewater is discharged outside, so that secondary pollution is caused. Therefore, the development of the desulfurization wastewater zero-discharge treatment technology is more and more emphasized.
Among the various development directions of the desulfurization wastewater zero-discharge treatment process, the evaporative crystallization method is the main treatment process concerned by research and development personnel in the industry at present. Although the evaporative crystallization method can reduce the salt content of the effluent after the desulfurization wastewater treatment to a great extent theoretically, and even reach the near-zero-emission standard brick, the evaporative crystallization method has some inevitable defects in industrial practice.
The disadvantages are mainly reflected in the following two aspects:
firstly, the evaporative crystallization cost is high, and a large amount of energy is consumed by adopting the evaporative crystallization process, so the operation cost is extremely high; secondly, the wastewater is firstly subjected to reduction treatment by adopting membrane separation technologies such as reverse osmosis and the like, and concentrated water generated by membrane separation is evaporated and crystallized, so that the evaporation treatment load can be effectively reduced and the treatment cost can be saved. However, when membrane treatment processes such as RO and the like are adopted, strict pretreatment needs to be carried out on the wastewater, the softening pretreatment cost is extremely high and generally can reach 15-30 yuan/ton due to the fact that calcium and magnesium in the wastewater are high in concentration and calcium sulfate is in a supersaturated state, a large amount of precipitated sludge can be generated in the pretreatment process, and the treatment cost of the precipitated sludge is additionally increased.
In order to reduce the desulfurization wastewater zero-discharge treatment cost and popularize the process for treating the desulfurization wastewater by the evaporative crystallization method, the development of a low-cost desulfurization wastewater pretreatment method is very important in view of the defects and shortcomings of the existing desulfurization wastewater zero-discharge process.
SUMMERY OF THE UTILITY MODEL
In view of the above problems, it is an object of the present invention to provide a device for pretreating desulfurization waste water. By optimizing the softening pretreatment process before the desulfurization wastewater is subjected to evaporative crystallization, the cost for treating the desulfurization wastewater by adopting an evaporative crystallization method can be effectively reduced.
In order to achieve the purpose, the utility model adopts the technical proposal that:
an apparatus for pretreatment of desulfurization waste water, comprising, provided in the flow direction of desulfurization waste water:
the first-stage reactor is provided with a barium hydroxide adding unit and an organic sulfur or sulfide adding unit;
the secondary reactor is provided with a barium salt adding unit.
Further, the device also comprises a primary sedimentation tank arranged between the first-stage reactor and the second-stage reactor; a secondary sedimentation tank arranged at the downstream of the secondary reactor.
Further, the device also comprises a pretreatment system arranged upstream of the primary reactor.
Further, the pretreatment system comprises a COD treatment unit and/or a suspended matter treatment unit.
Furthermore, the primary reactor and the secondary reactor are both provided with stirring units. The stirring unit can be a mechanical stirring unit or an aeration stirring unit.
Furthermore, the primary reactor comprises a first reaction unit and a second reaction unit, the barium hydroxide adding unit is arranged in the first reaction unit, and the organic sulfur or sulfide adding unit is arranged in the second reaction unit.
Furthermore, flocculation reaction units are arranged between the primary reactor and the primary sedimentation tank and between the secondary reactor and the secondary sedimentation tank.
Further, the bottom of the primary sedimentation tank and the bottom of the secondary sedimentation tank are both provided with sludge discharge ports.
An apparatus for pretreatment of desulfurization waste water, comprising, provided in the flow direction of desulfurization waste water:
the first-stage reactor is provided with a barium hydroxide adding unit and a barium salt adding unit;
the second-stage reactor is provided with an organic sulfur or sulfide adding unit.
Through taking above-mentioned technical scheme, the utility model discloses abandon the route that removes magnesium and calcium simultaneously among the traditional softening treatment, adopt barium hydroxide and barium chloride to jointly remove the weight and get rid of the method of sulfate radical, when getting rid of heavy metal in the waste water, effectively avoid the calcium sulfate scale deposit problem among the follow-up waste water concentration treatment, have that simple process, medicament input volume are few, the running cost is low, the mud production volume is few and easily the advantage that combines together with other technologies. Is particularly suitable for treating high-chlorine high-calcium desulfurization wastewater. And the dosage of the medicament can be reduced, so that the cost of the softening pretreatment of the desulfurization wastewater can be greatly reduced, and the process popularization of the desulfurization wastewater treatment by an evaporative crystallization method is facilitated.
Drawings
Fig. 1 is a schematic view of a device for pretreating desulfurization wastewater in an embodiment of the present invention.
Fig. 2 is a schematic diagram of the arrangement of a first-order reaction in another embodiment of the present invention.
Description of reference numerals: 1-a first-stage reactor, 2-a primary sedimentation tank, 3-a sludge discharge port, 4-a secondary reactor, 5-a secondary sedimentation tank and 6-a sludge discharge port.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments and examples.
As shown in fig. 1, in one embodiment, there is provided a desulfurization waste water treatment apparatus, which is arranged in accordance with a desulfurization waste water flow direction as follows: comprises a primary reactor 1, a primary sedimentation tank 2, a secondary reactor 4 and a secondary sedimentation tank 5, wherein the bottoms of the primary sedimentation tank 2 and the secondary sedimentation tank 6 are respectively provided with a sludge discharge port 3 and a sludge discharge port 6. Heavy metal sludge can be separated and treated independently by arranging the primary sedimentation tank and the secondary sedimentation tank, and the sludge treatment cost is favorably reduced.
In an embodiment not shown, the desulfurized waste water can be suitably pretreated before entering the reactor 1. The pretreatment system can adopt one or more treatment methods including COD treatment, suspended solid treatment and the like to pretreat the desulfurization wastewater, the selection of the pretreatment and the treatment method adopted by the specific pretreatment can be adjusted by combining the actual process requirements and the components of the desulfurization wastewater, and the details are not repeated herein, can be regarded as a common treatment mode of the desulfurization wastewater, and are not necessarily related to the core gist of the application.
As shown in the figure, the primary reactor 1 is provided with a stirring system which can adopt mechanical stirring and also can adopt aeration stirring for ensuring the uniform water quality in the reactor.
The primary reactor 1 is provided with a medicament adding system, and the medicaments A and B are respectively barium hydroxide and organic sulfur and are used for removing heavy metals and partial sulfate radicals in wastewater. The organic sulfur mainly removes mercury, and sulfides such as sodium sulfide and the like can be adopted, but the organic sulfur has good application effect and is easy to operate, other heavy metals are mainly removed through barium hydroxide, the adding sequence is A, B and then B, and the organic sulfur can also remove other heavy metals, but the organic sulfur is very expensive.
In another embodiment, the first-stage reactor may be configured as a dual reactor as shown in fig. 2, and the agent a and the agent B are sequentially added for performing the barium hydroxide heavy removal reaction and the organic sulfur heavy removal reaction, respectively.
In addition, a flocculation reaction system can be arranged between the primary reactor 1 and the primary sedimentation tank 2 according to requirements so as to improve the sludge sedimentation effect. Flocculation reagents are also known and will not be described further herein.
The sludge discharged from the sludge discharge port 3 is further treated after dehydration and drying; the sludge discharged from the sludge discharge port 6 is sent to the slurry of the desulfurizing tower or discharged to the gypsum dewatering machine.
The secondary reactor 4 is also provided with a stirring system and a medicament adding device.
The stirring system can adopt mechanical stirring or aeration stirring to ensure the uniform water quality in the reactor;
and the agent C is a barium salt, preferably barium chloride, and is used for removing residual sulfate radicals in the wastewater.
A flocculation reaction system can be arranged between the secondary reactor 4 and the secondary sedimentation tank 5 according to requirements so as to improve the sludge sedimentation efficiency.
The method for pretreating desulfurization wastewater by using the device can be realized by the following steps:
the desulfurization waste water firstly enters a first-stage reactor 1, barium hydroxide and organic sulfur agents are added into the reactor, the pH value of the waste water is adjusted to be about 9.5, heavy metals in the waste water are precipitated, and meanwhile, partial sulfate radicals in the waste water are combined with barium ions to form barium sulfate precipitates. The above-mentioned pH adjustment value is a preferable value under certain conditions, and actually, the adjustment range of the pH value may be set to 8.5 to 10 as required.
The effluent of the primary reactor 1 enters a primary sedimentation tank 2, sludge-water separation is realized under the action of gravity, the generated sludge is discharged through a sludge discharge port 3, is dewatered and dried, is further treated, and the supernatant enters a secondary reactor 4.
In order to improve the sludge settling property, the desulfurization wastewater can be subjected to flocculation reaction before entering the primary sedimentation tank 2 from the primary reactor 1.
Barium salt, preferably barium chloride, is added into the secondary reactor 4, so that sulfate radicals in the wastewater react to generate barium sulfate, the sulfate radicals are reduced to a required level, and the wastewater is ensured not to be obviously scaled in the subsequent concentration treatment.
The effluent of the secondary reactor 4 enters a secondary sedimentation tank 5, after mud-water separation, the supernatant is further treated, and the sludge generated in the secondary sedimentation tank 5 is discharged to a desulfurizing tower slurry or a gypsum dehydrator through a sludge discharge port 6.
Likewise, a flocculation reaction system may be provided between the secondary reactor 4 and the secondary sedimentation tank 5.
The method can be adjusted, and the device also performs adaptive adjustment: the scheme is as follows:
the desulfurization wastewater firstly enters a primary reactor, barium hydroxide and barium chloride agents are added into the reactor, the adding amount of the two agents is reasonably set, the pH value of the wastewater is adjusted to be about 9.5, heavy metals in the wastewater are precipitated, and meanwhile, partial sulfate radicals in the wastewater react to generate barium sulfate precipitates, so that the sulfate radicals in the wastewater are reduced to a target level. The adding amount of barium chloride is flexibly determined according to the requirements of the subsequent concentration process, and mainly controls the concentration of residual sulfate radicals in the wastewater.
And the desulfurization wastewater can be pretreated properly and then enters a primary reactor according to actual needs.
The effluent from the first stage reactor can be directly fed into the second stage reactor.
Organic sulfur is added into the secondary reactor to further remove heavy metals such as mercury in the wastewater.
And (3) the effluent of the secondary reactor enters a secondary sedimentation tank, after mud-water separation, the supernatant is further treated, and the sludge generated in the secondary sedimentation tank is subjected to subsequent treatment through the sludge generated in a sludge discharge port.
The feasibility and the superiority of the device and the method are verified through the practical experimental process. The experimental procedure was as follows:
taking actual desulfurization wastewater of a certain power plant, wherein the pH of raw water is 6.8, and the concentration of suspended matters in the wastewater is about 20000mg/L, firstly, removing the suspended matters in the wastewater through simple filtration, wherein the content of calcium ions in the wastewater is about 2600mg/L, the content of magnesium ions in the wastewater is 600mg/L, and the concentration of sulfate radicals in the wastewater is 1000 mg/L. It should be noted that heavy metal treatment is a conventional means in desulfurization wastewater treatment, and is not the focus of the present application, which focuses on the overall pretreatment cost, and therefore, heavy metal content is not provided herein. The following two sets of experiments were performed, respectively:
experiment I, adopting a traditional pretreatment process, namely a lime milk + organic sulfur + soda softening method, firstly adding lime milk (suspension with the mass concentration of 5%) into 1000mL of wastewater to adjust the pH of the wastewater to 11.5, simultaneously stirring the wastewater to ensure full and uniform reaction, after reacting for 15min, then adding organic sulfur and sodium carbonate (solution with the mass concentration of 10%) into the wastewater, producing magnesium hydroxide precipitate by magnesium ions in the wastewater and entering the sludge, reducing the calcium ion concentration in the wastewater to 20mg/L after flocculation precipitation treatment of the wastewater, discharging heavy metals in the wastewater up to the standard, then adding hydrochloric acid to adjust the pH of the wastewater back to 9.5, and the result shows that the dosage of the medicament is 4.0g/L of the lime milk, 50mg/L of the organic sulfur and 10.40g/L of the soda, and the consumption of the hydrochloric acid is 3 g/L. According to the market price, the total cost of the required medicament is about 24.1 yuan/ton, and the total cost of the required medicament is 300 yuan/ton, 500 yuan/ton, 120000 yuan/ton and 1500 yuan/ton respectively of hydrochloric acid (30%), lime, organic sulfur (100%) and soda ash. After two stages of precipitation (20 minutes for both precipitation times), the total volume of precipitated sludge was determined to be about 230 mL. The treated wastewater can meet the requirement of inlet water hardness in membrane concentration treatment.
Experiment two: adopt the utility model provides a process, after waste water got rid of most suspended solids through prefiltering, to adding barium hydroxide solution (mass concentration 2%) in the 1000mL waste water, adjust waste water pH to 9.5, then add organic sulfur solution, after the reaction 10min, after 5min with flocculating agent and coagulant aid reaction to adding in the waste water, survey the mud volume behind static 15 minutes, then add barium chloride in the filtrating behind the waste water filtration, after the reaction 10min, after 5min with flocculating agent and coagulant aid reaction to adding in the waste water, then static 15 minutes, survey supernatant sulfate radical and heavy metal concentration and deposit the mud volume.
The results show that when the sulfate radical in the wastewater is reduced to 20mg/L and the heavy metal reaches the standard and is discharged, the adding amount of barium hydroxide is 0.05g/L, the adding amount of barium chloride is 3.05g/L, the adding amount of organic sulfur is 50mg/L, and the cost of the water treatment agent per ton is about 14 yuan according to the market price of 2600 yuan/ton of barium chloride dihydrate, 4500 yuan/ton of barium hydroxide and 120000 yuan/ton of organic sulfur. Through determination, after 15min of precipitation, the volume of the first-stage precipitated sludge is 50mL, and the volume of the second-stage precipitated sludge is about 20 mL.
Experiment three: adopt the utility model discloses the technology, waste water is after the prefiltering gets rid of most suspended solid, to adding barium hydroxide solution (mass concentration 2%) in the 1000mL waste water, adjust waste water pH to 9.5, then add barium chloride (mass concentration 10%) solution, after reaction 10min, to adding organic sulfur in the waste water, after reaction 10min, after adding flocculating agent and coagulant aid reaction 5min in the waste water, then deposit and clarify after 15min, survey supernatant sulfate radical and heavy metal concentration and deposit the mud volume.
Tests show that when the sulfate radical in the wastewater is reduced to 20mg/L and heavy metals reach the standard and are discharged, the adding amount of barium hydroxide is 0.05g/L, the adding amount of barium chloride is 3.15g/L, the adding amount of organic sulfur is 50mg/L, and the cost of the water treatment agent per ton is about 14.2 yuan according to the market price of 2600 yuan/ton of barium chloride dihydrate, 4500 yuan/ton of barium hydroxide and 120000 yuan/ton of organic sulfur. Through determination, the total volume of the sludge after precipitation in the 15min sedimentation tank is about 65 mL. The raw treated wastewater can meet the water inlet requirement of membrane concentration treatment.
It can be seen from the above embodiment that, adopting the utility model discloses a desulfurization waste water is handled to technology, and the medicament expense is only 14 yuan/ton, reduces by a wide margin than the 24.1 yuan/ton of traditional handicraft, and the sludge volume that just produces also reduces by a wide margin, is favorable to reducing follow-up sludge treatment load and treatment cost.
It is to be understood that the embodiments described are only some embodiments of the invention, and not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
Claims (6)
1. The utility model provides a device that desulfurization waste water was pretreated, its characterized in that includes along desulfurization waste water flow direction setting:
a first stage reactor comprising a first reaction unit and a second reaction unit, wherein,
the first reaction unit is provided with a barium hydroxide adding unit and is used for reacting the desulfurization wastewater with the barium hydroxide added by the barium hydroxide adding unit;
the second reaction unit is provided with an organic sulfur or sulfide adding unit and is used for the reaction of the desulfurization wastewater and the organic sulfur or sulfide added by the organic sulfur or sulfide adding unit;
the primary sedimentation tank is used for carrying out mud-water separation on the desulfurization wastewater from the primary reactor;
the secondary reactor is provided with a barium salt adding unit and is used for reacting the desulfurization wastewater from the primary sedimentation tank with the barium salt added by the barium salt adding unit;
and the secondary sedimentation tank is used for carrying out sludge-water separation on the desulfurization wastewater from the secondary reactor.
2. The apparatus for pretreatment of desulfurization wastewater of claim 1, wherein flocculation reaction units are disposed between the primary reactor and the primary sedimentation tank, and between the secondary reactor and the secondary sedimentation tank.
3. The apparatus for pretreatment of desulfurization wastewater of claim 1, wherein sludge discharge ports are provided at the bottoms of the primary sedimentation tank and the secondary sedimentation tank.
4. The apparatus for pretreatment of desulfurization wastewater of claim 1, further comprising a pretreatment system disposed upstream of the primary reactor.
5. The apparatus for pretreatment of desulfurization wastewater of claim 4, wherein the pretreatment system comprises a COD treatment unit and/or a suspended matter treatment unit.
6. The apparatus for pretreating desulfurization waste water according to claim 1, wherein the primary reactor and the secondary reactor are each provided with a stirring unit, and the stirring unit is a mechanical stirring unit or an aeration stirring unit.
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